Structures of incommensurate and commensurate composite crystals NaxCuO2 (x = 1.58, 1.6, 1.62)

van Smaalen, S.; Dinnebier, R.; Sofin, M.; Jansen, M.

doi:10.1107/S0108768106039462

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Structures of incommensurate and commensurate composite crystals Na_xCuO₂ (x = 1.58, 1.6, 1.62)

S. van Smaalen, R. Dinnebier, M. Sofin and M. Jansen

Na_xCuO₂ (x ≃ 1.6) has been synthesized for different compositions x, resulting in both commensurate and incommensurate composite crystals. The crystal structures are reported for two incommensurate compounds (x = 1.58 and 1.62) determined by Rietveld refinements against X-ray powder diffraction data. The incommensurate compounds and commensurate Na₈Cu₅O₁₀ (x = 1.6) are found to possess similar structures, with valence fluctuations of Cu²⁺/Cu³⁺ as the origin of the modulations of the CuO₂ subsystems; the displacive modulations of Na being defined by the closest Na—O contacts between the subsystems. A comparison of the structure models obtained from single-crystal X-ray diffraction, synchrotron-radiation X-ray powder diffraction and X-ray powder diffraction with Cu Kα₁ radiation indicates that single-crystal X-ray diffraction is by far the most accurate method, while powder diffraction with radiation from an X-ray tube provides the least accurate structure model.

Keywords: incommensurate composite crystal; powder diffraction; Rietveld refinement.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S0108768106039462/ck5018sup1.cif Contains datablocks global, I, II, III
	Rietveld powder data file (CIF format) https://doi.org/10.1107/S0108768106039462/ck5018Isup2.rtv Contains datablock I
	Structure factor file (CIF format) https://doi.org/10.1107/S0108768106039462/ck5018IIsup3.hkl Contains datablock II
	Rietveld powder data file (CIF format) https://doi.org/10.1107/S0108768106039462/ck5018IIIsup4.rtv Contains datablock III

Computing details top

Cell refinement: (Jana2000; Petricek and Dusek, 2000) for (I). Program(s) used to solve structure: (Jana2000; Petricek and Dusek, 2000) for (I). For all compounds, program(s) used to refine structure: (Jana2000; Petricek and Dusek, 2000). Molecular graphics: (Diamond 3, Brandenburg, 2004) for (I). For all compounds, software used to prepare material for publication: (Jana2000; Petricek and Dusek, 2000).

Figures top

(I) sodium copper oxide top

Crystal data top

CuNa_1.57664O₂	V = 121.73 (1) Å³
M_r = 661.6	Z = 2
Monoclinic, C2/m(0β0)s0†	F(000) = 125
q = 0.78832b*‡	D_x = 9.023 Mg m⁻³
a = 8.24153 (4) Å	Synchrotron radiation, λ = 0.65046 Å
b = 2.78589 (2) Å	T = 293 K
c = 5.71687 (3) Å	?, ? × ? × ? mm
β = 111.9698 (5)°

;

Data collection top

Radiation source: NSLS, Brookhaven National Laboratory

2θ_min = 5°, 2θ_max = 43.404°, 2θ_step = 0.004°

Refinement top

R_p = 0.075	36 parameters
R_wp = 0.101	0 restraints
R_exp = 0.050	Weighting scheme based on measured s.u.'s
R(F) = 0.048	(Δ/σ)_max = 0.295
χ² = NOT FOUND	Background function: 4 Legendre polynoms
9602 data points	Preferred orientation correction: none
Profile function: Pseudo-Voigt

Crystal data top

CuNa_1.57664O₂	β = 111.9698 (5)°
M_r = 661.6	V = 121.73 (1) Å³
Monoclinic, C2/m(0β0)s0†	Z = 2
q = 0.78832b*‡	Synchrotron radiation, λ = 0.65046 Å
a = 8.24153 (4) Å	T = 293 K
b = 2.78589 (2) Å	?, ? × ? × ? mm
c = 5.71687 (3) Å

;

Data collection top

2θ_min = 5°, 2θ_max = 43.404°, 2θ_step = 0.004°

Refinement top

R_p = 0.075	9602 data points
R_wp = 0.101	36 parameters
R_exp = 0.050	0 restraints
R(F) = 0.048	(Δ/σ)_max = 0.295
χ² = NOT FOUND

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cu1	0	0.5	0	0.0038 (2)*
O1	0.0493 (3)	0	0.2416 (3)	0.0091 (7)*
Na1	−0.1512 (3)	0.25	0.3832 (4)	0.0141 (6)*

Bond lengths (Å) top

	Average	Minimum	Maximum
Cu1—Cu1ⁱ	2.790 (2)	2.763 (4)	2.816 (4)
Cu1—Cu1ⁱⁱ	2.790 (2)	2.764 (4)	2.816 (4)
Cu1—Cu1ⁱⁱⁱ	4.3546 (15)	4.217 (2)	4.494 (2)
Cu1—Cu1^iv	4.3543 (15)	4.217 (2)	4.494 (2)
Cu1—Cu1^v	4.3551 (15)	4.217 (2)	4.494 (2)
Cu1—Cu1^vi	4.3554 (15)	4.217 (2)	4.494 (2)
Cu1—O1ⁱ	4.376 (8)	4.314 (6)	4.490 (11)
Cu1—O1^vii	4.714 (9)	4.599 (10)	4.791 (5)
Cu1—O1	1.899 (8)	1.841 (7)	1.961 (8)
Cu1—O1^viii	4.715 (9)	4.599 (9)	4.791 (5)
Cu1—O1ⁱⁱ	1.898 (8)	1.841 (7)	1.962 (8)
Cu1—O1^ix	4.376 (8)	4.314 (6)	4.490 (11)
Cu1—O1^x	4.532 (6)	4.271 (12)	4.878 (12)
Cu1—O1^iv	4.427 (9)	4.392 (18)	4.476 (18)
Cu1—O1^v	5.050 (8)	4.908 (7)	5.260 (7)
Cu1—O1^vi	4.214 (8)	3.989 (16)	4.391 (15)
Cu1—O1^xi	5.051 (8)	4.908 (7)	5.260 (7)
Cu1—O1^xii	4.376 (8)	4.314 (6)	4.490 (11)
Cu1—O1^xiii	1.899 (8)	1.841 (7)	1.961 (8)
Cu1—O1^xiv	4.715 (9)	4.599 (10)	4.791 (5)
Cu1—O1^xv	1.898 (8)	1.841 (7)	1.962 (8)
Cu1—O1^xvi	4.714 (9)	4.599 (9)	4.791 (5)
Cu1—O1^xvii	4.377 (8)	4.314 (6)	4.490 (11)
Cu1—O1^xviii	5.049 (8)	4.908 (7)	5.260 (7)
Cu1—O1^xix	4.213 (8)	3.989 (16)	4.391 (15)
Cu1—O1^xx	5.049 (8)	4.908 (7)	5.260 (7)
Cu1—O1^xxi	4.427 (9)	4.392 (18)	4.476 (18)
Cu1—O1^xxii	4.534 (6)	4.271 (12)	4.878 (12)
Cu1—Na1^vii	816.4 (11)	3.084 (4)	5.162 (6)
Cu1—Na1^viii	734.9 (11)	3.075 (3)	4.248 (8)
Cu1—Na1^xxiii	1159.5 (10)	4.232 (5)	6.972 (6)
Cu1—Na1ⁱ	1317.8 (11)	4.952 (7)	8.515 (5)
Cu1—Na1	755.7 (13)	2.902 (5)	4.952 (7)
Cu1—Na1ⁱⁱ	670.3 (14)	2.899 (5)	4.058 (5)
Cu1—Na1^ix	1120.9 (11)	4.058 (5)	6.861 (6)
Cu1—Na1^vi	770.7 (10)	3.127 (4)	5.181 (5)
Cu1—Na1^xi	648.8 (10)	2.641 (9)	4.233 (5)
Cu1—Na1^xxiv	1146.2 (9)	4.233 (5)	7.515 (6)
Cu1—Na1^xiii	1011.4 (11)	3.834 (5)	6.324 (5)
Cu1—Na1^xv	630.0 (13)	2.899 (5)	3.834 (5)
Cu1—Na1^xvii	863.0 (13)	3.201 (10)	5.922 (5)
Cu1—Na1^xiv	1055.5 (10)	4.172 (5)	6.565 (5)
Cu1—Na1^xvi	697.5 (11)	3.075 (3)	4.172 (5)
Cu1—Na1^xxv	919.1 (11)	3.738 (8)	6.149 (5)
Cu1—Na1^xix	995.9 (9)	3.365 (4)	6.564 (5)
Cu1—Na1^xx	632.8 (10)	2.641 (9)	3.374 (6)
Cu1—Na1^xxvi	854.5 (10)	3.183 (9)	5.329 (5)
O1—O1ⁱ	2.789 (11)	2.668 (14)	3.008 (15)
O1—O1ⁱⁱ	2.789 (11)	2.668 (14)	3.008 (15)
O1—O1ⁱⁱⁱ	4.355 (13)	4.267 (11)	4.484 (16)
O1—O1^iv	4.354 (13)	4.267 (11)	4.484 (16)
O1—O1^v	4.355 (13)	4.267 (11)	4.484 (16)
O1—O1^vi	4.355 (13)	4.267 (11)	4.484 (16)
O1—O1^xii	3.795 (11)	3.729 (13)	3.862 (12)
O1—O1^xxvii	4.354 (13)	4.116 (11)	4.474 (15)
O1—O1^xiii	2.575 (11)	2.50 (2)	2.654 (14)
O1—O1^xiv	3.346 (13)	3.301 (17)	3.39 (2)
O1—O1^xv	3.795 (11)	3.729 (13)	3.862 (12)
O1—O1^xvi	4.353 (13)	4.116 (11)	4.474 (15)
O1—O1^xviii	4.871 (11)	4.633 (13)	5.051 (13)
O1—O1^xix	4.871 (11)	4.633 (13)	5.051 (13)
O1—O1^xxviii	3.783 (10)	3.640 (8)	4.067 (12)
O1—O1^xxii	3.784 (10)	3.640 (8)	4.067 (12)
O1—Na1^vii	952.7 (19)	4.578 (14)	5.444 (11)
O1—Na1^viii	1076 (2)	4.578 (14)	6.169 (9)
O1—Na1ⁱ	998 (2)	3.507 (11)	6.988 (7)
O1—Na1	495 (2)	2.230 (11)	3.507 (11)
O1—Na1ⁱⁱ	695 (2)	2.257 (12)	4.620 (8)
O1—Na1^ix	1300.7 (18)	4.620 (8)	7.808 (8)
O1—Na1^v	1003.5 (19)	3.709 (9)	6.400 (7)
O1—Na1^vi	542 (2)	2.189 (7)	3.709 (9)
O1—Na1^xi	706.7 (19)	2.189 (7)	4.981 (8)
O1—Na1^xxiv	1344.1 (18)	4.981 (8)	8.486 (8)
O1—Na1^xiii	980 (2)	4.193 (12)	5.889 (10)
O1—Na1^xv	841 (2)	3.93 (2)	4.693 (14)
O1—Na1^xvii	1208 (2)	4.693 (14)	7.635 (9)
O1—Na1^xxvii	1293.3 (17)	4.749 (8)	7.933 (8)
O1—Na1^xiv	680.0 (19)	2.250 (10)	4.749 (8)
O1—Na1^xvi	481.1 (19)	2.220 (9)	3.246 (9)
O1—Na1^xxv	989.6 (18)	3.246 (9)	6.769 (7)
O1—Na1^xix	941.6 (17)	3.799 (7)	5.978 (8)
O1—Na1^xx	826.8 (17)	3.756 (15)	4.811 (7)
O1—Na1^xxvi	1184.5 (18)	4.781 (10)	7.023 (8)
O1—Na1^xxix	1062 (2)	4.480 (8)	6.457 (10)
O1—Na1^xxx	960 (2)	4.480 (8)	5.339 (14)
O1—Na1^xxii	1091 (2)	4.625 (10)	6.823 (9)
O1—Na1^xxxi	962.3 (19)	4.446 (6)	5.236 (11)
Na1—Na1ⁱ	3.553 (7)	3.059 (10)	4.233 (10)
Na1—Na1ⁱⁱ	3.549 (7)	3.059 (10)	4.233 (10)
Na1—Na1ⁱⁱⁱ	5.444 (9)	4.811 (11)	5.758 (7)
Na1—Na1^iv	4.163 (9)	3.639 (18)	4.617 (17)
Na1—Na1^xxxii	5.444 (9)	4.811 (11)	5.758 (7)
Na1—Na1^v	5.444 (9)	4.811 (11)	5.758 (7)
Na1—Na1^vi	4.161 (9)	3.639 (18)	4.617 (17)
Na1—Na1^xi	5.440 (9)	4.811 (11)	5.758 (7)
Na1—Na1^xiv	2.982 (8)	2.550 (6)	3.197 (9)
Na1—Na1^xvi	2.980 (8)	2.550 (6)	3.197 (9)
Na1—Na1^xix	4.453 (8)	4.347 (9)	4.534 (7)
Na1—Na1^xxix	3.064 (10)	3.029 (9)	3.088 (9)
Na1—Na1^xx	4.453 (8)	4.347 (9)	4.534 (7)
Na1—Na1^xxx	3.064 (10)	3.029 (9)	3.088 (9)

Symmetry codes: (i) x₁, x₂−1, x₃, x₄; (ii) x₁, x₂+1, x₃, x₄; (iii) x₁−1/2, x₂−1/2, x₃, x₄; (iv) x₁−1/2, x₂+1/2, x₃, x₄; (v) x₁+1/2, x₂−1/2, x₃, x₄; (vi) x₁+1/2, x₂+1/2, x₃, x₄; (vii) x₁, x₂, x₃−1, x₄; (viii) x₁, x₂+1, x₃−1, x₄; (ix) x₁, x₂+2, x₃, x₄; (x) x₁−1/2, x₂+1/2, x₃−1, x₄; (xi) x₁+1/2, x₂+3/2, x₃, x₄; (xii) −x₁, −x₂−1, −x₃, −x₄; (xiii) −x₁, −x₂, −x₃, −x₄; (xiv) −x₁, −x₂, −x₃+1, −x₄; (xv) −x₁, −x₂+1, −x₃, −x₄; (xvi) −x₁, −x₂+1, −x₃+1, −x₄; (xvii) −x₁, −x₂+2, −x₃, −x₄; (xviii) −x₁−1/2, −x₂−1/2, −x₃, −x₄; (xix) −x₁−1/2, −x₂+1/2, −x₃, −x₄; (xx) −x₁−1/2, −x₂+3/2, −x₃, −x₄; (xxi) −x₁+1/2, −x₂+1/2, −x₃, −x₄; (xxii) −x₁+1/2, −x₂+1/2, −x₃+1, −x₄; (xxiii) x₁, x₂+2, x₃−1, x₄; (xxiv) x₁+1/2, x₂+5/2, x₃, x₄; (xxv) −x₁, −x₂+2, −x₃+1, −x₄; (xxvi) −x₁−1/2, −x₂+5/2, −x₃, −x₄; (xxvii) −x₁, −x₂−1, −x₃+1, −x₄; (xxviii) −x₁+1/2, −x₂−1/2, −x₃+1, −x₄; (xxix) −x₁−1/2, −x₂+1/2, −x₃+1, −x₄; (xxx) −x₁−1/2, −x₂+3/2, −x₃+1, −x₄; (xxxi) −x₁+1/2, −x₂+3/2, −x₃+1, −x₄; (xxxii) x₁−1/2, x₂+3/2, x₃, x₄.

(II) top

Crystal data top

Cu₅Na₈O₁₀	V = 121.73 Å³
M_r = 661.6	Z = 1
Monoclinic, C2/m(0β0)s0†	F(000) = 125
q = 0.80000b*‡	D_x = 9.023 Mg m⁻³
a = 8.2417 Å	X-ray radiation, λ = 0.70926 Å
b = 2.7859 Å	µ = 22.32 mm⁻¹
c = 5.7167 Å	T = 293 K
β = 111.9709°	× × mm

;

Data collection top

5656 independent reflections	k = ?→?
4523 reflections with I > 3σ(I)	l = ?→?
h = ?→?

Refinement top

Refinement on F	5656 reflections
R[F² > 2σ(F²)] = 0.035	107 parameters
wR(F²) = 0.033	Weighting scheme based on measured s.u.'s w = 1/σ²(F)
S = 2.95	(Δ/σ)_max = 0.002

Crystal data top

Cu₅Na₈O₁₀	β = 111.9709°
M_r = 661.6	V = 121.73 Å³
Monoclinic, C2/m(0β0)s0†	Z = 1
q = 0.80000b*‡	X-ray radiation, λ = 0.70926 Å
a = 8.2417 Å	µ = 22.32 mm⁻¹
b = 2.7859 Å	T = 293 K
c = 5.7167 Å	× × mm

;

Data collection top

5656 independent reflections

4523 reflections with I > 3σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.035	5656 reflections
wR(F²) = 0.033	107 parameters
S = 2.95

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cu1	0	0.5	0	0.0107
O1	0.05204	0	0.242277	0.0161
Na1	−0.154182	0.25	0.377855	0.0268

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.012659	0.010929	0.008165	0	0.003339	0
O1	0.023003	0.014862	0.009429	0	0.004993	0
Na1	0.021659	0.042864	0.016004	0	0.007236	0

Bond lengths (Å) top

	Average	Minimum	Maximum
Cu1—Cu1ⁱ	2.7895	2.7577	2.8181
Cu1—Cu1ⁱⁱ	2.7895	2.7577	2.8181
Cu1—O1	1.8991	1.8579	1.9298
Cu1—O1ⁱⁱ	1.8991	1.8579	1.9298
Cu1—Na1ⁱⁱⁱ	17.5745	3.0599	4.1968
Cu1—Na1	20.3621	3.2115	5.1372
Cu1—Na1ⁱⁱ	15.7315	2.8961	3.776
Cu1—Na1^iv	20.5305	3.2528	5.1985
Cu1—Na1^v	15.6325	2.738	3.3056
Cu1—O11	1.9004	1.8332	1.9504
Cu1—O11ⁱⁱ	1.9004	1.8332	1.9504
Cu1—Na11ⁱⁱ	16.2516	2.8958	3.8568
Cu1—Na11^vi	19.3148	3.0749	4.7487
Cu1—Na11^vii	18.0009	3.1054	4.1987
Cu1—Na11^viii	15.6102	2.8067	3.4583
Cu1—Na11^ix	19.4405	3.2627	5.1377
O1—O1ⁱ	2.7886	2.709	2.8845
O1—O1ⁱⁱ	2.7886	2.709	2.8845
O1—Na1	13.4019	2.2948	3.6968
O1—Na1ⁱⁱ	15.5059	2.3242	4.3988
O1—Na1^iv	14.3695	2.2962	3.7564
O1—Na1^v	15.8104	2.2962	3.8109
O1—O11	2.5776	2.5176	2.654
O1—O11^x	3.3653	3.3482	3.3886
O1—Na11^x	18.6881	2.3551	4.8118
O1—Na11^vii	11.6155	2.2979	2.3551
O1—Na11^xi	21.7372	3.0006	5.4042
Na1—Na1ⁱ	3.4932	3.0793	3.9071
Na1—Na1ⁱⁱ	3.4932	3.0793	3.9071
Na1—O11^x	9.3842	2.2772	2.4236
Na1—O11^vii	10.7287	2.3301	3.6216
Na1—Na11^x	2.9994	2.7945	3.1618
Na1—Na11^vii	2.9994	2.7945	3.1618
Na1—Na11^xii	3.0505	2.9911	3.1095
Na1—Na11^xiii	3.0505	2.9911	3.1095
O11—O11ⁱ	2.792	2.6948	3
O11—O11ⁱⁱ	2.792	2.6948	3
O11—Na11	19.025	2.5664	4.7373
O11—Na11ⁱⁱ	11.9068	2.3115	2.5664
O11—Na11^vi	22.0161	3.1755	5.5575
O11—Na11^xiv	19.4868	2.7714	5.1699
O11—Na11^viii	12.0532	2.2831	2.7714
Na11—Na11ⁱ	3.4961	3.0733	3.8669
Na11—Na11ⁱⁱ	3.4961	3.0733	3.8669

Symmetry codes: (i) x₁, x₂−1, x₃, x₄; (ii) x₁, x₂+1, x₃, x₄; (iii) x₁, x₂+1, x₃−1, x₄; (iv) x₁+1/2, x₂+1/2, x₃, x₄; (v) x₁+1/2, x₂+3/2, x₃, x₄; (vi) x₁, x₂+2, x₃, x₄; (vii) x₁, x₂+1, x₃+1, x₄; (viii) x₁−1/2, x₂+3/2, x₃, x₄; (ix) x₁−1/2, x₂+5/2, x₃, x₄; (x) x₁, x₂, x₃+1, x₄; (xi) x₁, x₂+2, x₃+1, x₄; (xii) x₁−1/2, x₂+1/2, x₃+1, x₄; (xiii) x₁−1/2, x₂+3/2, x₃+1, x₄; (xiv) x₁−1/2, x₂+1/2, x₃, x₄.

(III) top

Crystal data top

CuNa_1.61689O₂	V = 122.11 (1) Å³
M_r = 661.6	Z = 2
Monoclinic, C2/m(0β0)s0†	F(000) = 126
q = 0.80844(3)b*‡	D_x = 8.994 Mg m⁻³
a = 8.23682 (15) Å	X-ray radiation, λ = 1.54059 Å
b = 2.79269 (4) Å	T = 293 K
c = 5.71224 (10) Å	?, ? × ? × ? mm
β = 111.6696 (9)°

;

Data collection top

2θ_min = 9.987°, 2θ_max = 79.977°, 2θ_step = 0.01°

Refinement top

R_p = 0.094	Profile function: Pseudo-Voigt
R_wp = 0.122	37 parameters
R_exp = 0.063	Weighting scheme based on measured s.u.'s
R(F) = 0.056	(Δ/σ)_max = 0.049
χ² = NOT FOUND	Background function: 5 Legendre polynoms
7000 data points	Preferred orientation correction: none

Crystal data top

CuNa_1.61689O₂	β = 111.6696 (9)°
M_r = 661.6	V = 122.11 (1) Å³
Monoclinic, C2/m(0β0)s0†	Z = 2
q = 0.80844(3)b*‡	X-ray radiation, λ = 1.54059 Å
a = 8.23682 (15) Å	T = 293 K
b = 2.79269 (4) Å	?, ? × ? × ? mm
c = 5.71224 (10) Å

;

Data collection top

2θ_min = 9.987°, 2θ_max = 79.977°, 2θ_step = 0.01°

Refinement top

R_p = 0.094	χ² = NOT FOUND
R_wp = 0.122	7000 data points
R_exp = 0.063	37 parameters
R(F) = 0.056

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cu1	0	0.5	0	0.0024 (4)*
O1	0.0526 (3)	0	0.2465 (5)	0.0208 (10)*
Na1	−0.1566 (4)	0.25	0.3717 (5)	0.0183 (9)*

Bond lengths (Å) top

	Average	Minimum	Maximum
Cu1—Cu1ⁱ	2.797 (3)	2.781 (4)	2.812 (4)
Cu1—Cu1ⁱⁱ	2.796 (3)	2.781 (4)	2.812 (4)
Cu1—O1	1.919 (10)	1.857 (12)	1.982 (10)
Cu1—O1ⁱⁱ	1.918 (10)	1.857 (12)	1.982 (10)
Cu1—O1ⁱⁱⁱ	1.919 (10)	1.857 (12)	1.982 (10)
Cu1—O1^iv	1.918 (10)	1.857 (12)	1.982 (10)
Cu1—Na1	376.3 (8)	2.876 (8)	4.854 (7)
Cu1—Na1ⁱⁱ	331.7 (8)	2.876 (8)	4.020 (9)
Cu1—Na1^v	318.7 (6)	2.548 (10)	3.927 (6)
Cu1—Na1^iv	312.9 (8)	2.876 (8)	3.805 (7)
Cu1—Na1^vi	313.0 (6)	2.548 (10)	3.366 (6)
O1—O1ⁱ	2.795 (13)	2.733 (16)	2.915 (16)
O1—O1ⁱⁱ	2.794 (13)	2.733 (16)	2.915 (16)
O1—O1ⁱⁱⁱ	2.625 (14)	2.54 (3)	2.711 (18)
O1—Na1	248.1 (14)	2.175 (13)	3.384 (12)
O1—Na1ⁱⁱ	345.2 (13)	2.214 (14)	4.592 (10)
O1—Na1^vii	266.2 (12)	2.147 (9)	3.710 (11)
O1—Na1^v	346.0 (12)	2.147 (9)	4.741 (9)
O1—Na1^viii	339.6 (12)	2.231 (13)	4.689 (9)
O1—Na1^ix	243.6 (12)	2.210 (12)	3.264 (11)
Na1—Na1^viii	3.038 (9)	2.656 (7)	3.228 (10)
Na1—Na1^ix	3.036 (9)	2.656 (7)	3.228 (10)

Symmetry codes: (i) x₁, x₂−1, x₃, x₄; (ii) x₁, x₂+1, x₃, x₄; (iii) −x₁, −x₂, −x₃, −x₄; (iv) −x₁, −x₂+1, −x₃, −x₄; (v) x₁+1/2, x₂+3/2, x₃, x₄; (vi) −x₁−1/2, −x₂+3/2, −x₃, −x₄; (vii) x₁+1/2, x₂+1/2, x₃, x₄; (viii) −x₁, −x₂, −x₃+1, −x₄; (ix) −x₁, −x₂+1, −x₃+1, −x₄.

Experimental details

	(I)	(II)	(III)
Crystal data
Chemical formula	CuNa_1.57664O₂	Cu₅Na₈O₁₀	CuNa_1.61689O₂
M_r	661.6	661.6	661.6
Crystal system, space group	Monoclinic, C2/m(0β0)s0†	Monoclinic, C2/m(0β0)s0‡	Monoclinic, C2/m(0β0)s0§
Temperature (K)	293	293	293
Wave vectors	q = 0.78832b*††	q = 0.80000b*‡‡	q = 0.80844(3)b*§§
a, b, c (Å)	8.24153 (4), 2.78589 (2), 5.71687 (3)	8.2417, 2.7859, 5.7167	8.23682 (15), 2.79269 (4), 5.71224 (10)
β (°)	111.9698 (5)	111.9709	111.6696 (9)
V (Å³)	121.73 (1)	121.73	122.11 (1)
Z	2	1	2
Radiation type	Synchrotron, λ = 0.65046 Å	X-ray, λ = 0.70926 Å	X-ray, λ = 1.54059 Å
µ (mm⁻¹)	–	22.32	–
Specimen shape, size (mm)	?, ? × ? × ?	× ×	?, ? × ? × ?

Data collection
Diffractometer	?	?	?
Specimen mounting	?	–	?
Data collection mode	?	–	?
Data collection method	?	?	?
Absorption correction	–	–	–
No. of measured, independent and observed reflections	–	?, 5656, 4523	–
R_int	–	?	–
θ values (°)	2θ_min = 5 2θ_max = 43.404 2θ_step = 0.004	θ_max = ?	2θ_min = 9.987 2θ_max = 79.977 2θ_step = 0.01

Refinement
R factors and goodness of fit	R_p = 0.075, R_wp = 0.101, R_exp = 0.050, R(F) = 0.048, χ² = NOT FOUND	R[F² > 2σ(F²)] = 0.035, wR(F²) = 0.033, S = 2.95	R_p = 0.094, R_wp = 0.122, R_exp = 0.063, R(F) = 0.056, χ² = NOT FOUND
No. of reflections/data points	9602	5656	7000
No. of parameters	36	107	37
No. of restraints	0	?	?
(Δ/σ)_max	0.295	0.002	0.049
Δρ_max, Δρ_min (e Å⁻³)	–	?, ?	–

† Symmetry operations: (1) x₁, x₂, x₃, x₄; (2) −x₁, x₂, −x₃, 1/2+x₄; (3) −x₁, −x₂, −x₃, −x₄; (4) x₁, −x₂, x₃, 1/2−x₄; (5) 1/2+x₁, 1/2+x₂, x₃, x₄; (6) 1/2−x₁, 1/2+x₂, −x₃, 1/2+x₄; (7) 1/2−x₁, 1/2−x₂, −x₃, −x₄; (8) 1/2+x₁, 1/2−x₂, x₃, 1/2−x₄.

‡ Symmetry operations: (1) x₁, x₂, x₃, x₄; (2) −x₁, x₂, −x₃, 1/2+x₄; (3) −x₁, −x₂, −x₃, −x₄; (4) x₁, −x₂, x₃, 1/2−x₄; (5) 1/2+x₁, 1/2+x₂, x₃, x₄; (6) 1/2−x₁, 1/2+x₂, −x₃, 1/2+x₄; (7) 1/2−x₁, 1/2−x₂, −x₃, −x₄; (8) 1/2+x₁, 1/2−x₂, x₃, 1/2−x₄.

§ Symmetry operations: (1) x₁, x₂, x₃, x₄; (2) −x₁, x₂, −x₃, 1/2+x₄; (3) −x₁, −x₂, −x₃, −x₄; (4) x₁, −x₂, x₃, 1/2−x₄; (5) 1/2+x₁, 1/2+x₂, x₃, x₄; (6) 1/2−x₁, 1/2+x₂, −x₃, 1/2+x₄; (7) 1/2−x₁, 1/2−x₂, −x₃, −x₄; (8) 1/2+x₁, 1/2−x₂, x₃, 1/2−x₄.

†† ;

‡‡ ;

§§ ;

Computer programs: (Jana2000; Petricek and Dusek, 2000), (Diamond 3, Brandenburg, 2004).

Selected bond lengths (Å) for (I) top

	Average	Minimum	Maximum
Cu1—Cu1ⁱ	2.790 (2)	2.763 (4)	2.816 (4)
Cu1—Cu1ⁱⁱ	2.790 (2)	2.764 (4)	2.816 (4)
Cu1—Cu1ⁱⁱⁱ	4.3546 (15)	4.217 (2)	4.494 (2)
Cu1—Cu1^iv	4.3543 (15)	4.217 (2)	4.494 (2)
Cu1—Cu1^v	4.3551 (15)	4.217 (2)	4.494 (2)
Cu1—Cu1^vi	4.3554 (15)	4.217 (2)	4.494 (2)
Cu1—O1ⁱ	4.376 (8)	4.314 (6)	4.490 (11)
Cu1—O1^vii	4.714 (9)	4.599 (10)	4.791 (5)
Cu1—O1	1.899 (8)	1.841 (7)	1.961 (8)
Cu1—O1^viii	4.715 (9)	4.599 (9)	4.791 (5)
Cu1—O1ⁱⁱ	1.898 (8)	1.841 (7)	1.962 (8)
Cu1—O1^ix	4.376 (8)	4.314 (6)	4.490 (11)
Cu1—O1^x	4.532 (6)	4.271 (12)	4.878 (12)
Cu1—O1^iv	4.427 (9)	4.392 (18)	4.476 (18)
Cu1—O1^v	5.050 (8)	4.908 (7)	5.260 (7)
Cu1—O1^vi	4.214 (8)	3.989 (16)	4.391 (15)
Cu1—O1^xi	5.051 (8)	4.908 (7)	5.260 (7)
Cu1—O1^xii	4.376 (8)	4.314 (6)	4.490 (11)
Cu1—O1^xiii	1.899 (8)	1.841 (7)	1.961 (8)
Cu1—O1^xiv	4.715 (9)	4.599 (10)	4.791 (5)
Cu1—O1^xv	1.898 (8)	1.841 (7)	1.962 (8)
Cu1—O1^xvi	4.714 (9)	4.599 (9)	4.791 (5)
Cu1—O1^xvii	4.377 (8)	4.314 (6)	4.490 (11)
Cu1—O1^xviii	5.049 (8)	4.908 (7)	5.260 (7)
Cu1—O1^xix	4.213 (8)	3.989 (16)	4.391 (15)
Cu1—O1^xx	5.049 (8)	4.908 (7)	5.260 (7)
Cu1—O1^xxi	4.427 (9)	4.392 (18)	4.476 (18)
Cu1—O1^xxii	4.534 (6)	4.271 (12)	4.878 (12)
Cu1—Na1^vii	816.4 (11)	3.084 (4)	5.162 (6)
Cu1—Na1^viii	734.9 (11)	3.075 (3)	4.248 (8)
Cu1—Na1^xxiii	1159.5 (10)	4.232 (5)	6.972 (6)
Cu1—Na1ⁱ	1317.8 (11)	4.952 (7)	8.515 (5)
Cu1—Na1	755.7 (13)	2.902 (5)	4.952 (7)
Cu1—Na1ⁱⁱ	670.3 (14)	2.899 (5)	4.058 (5)
Cu1—Na1^ix	1120.9 (11)	4.058 (5)	6.861 (6)
Cu1—Na1^vi	770.7 (10)	3.127 (4)	5.181 (5)
Cu1—Na1^xi	648.8 (10)	2.641 (9)	4.233 (5)
Cu1—Na1^xxiv	1146.2 (9)	4.233 (5)	7.515 (6)
Cu1—Na1^xiii	1011.4 (11)	3.834 (5)	6.324 (5)
Cu1—Na1^xv	630.0 (13)	2.899 (5)	3.834 (5)
Cu1—Na1^xvii	863.0 (13)	3.201 (10)	5.922 (5)
Cu1—Na1^xiv	1055.5 (10)	4.172 (5)	6.565 (5)
Cu1—Na1^xvi	697.5 (11)	3.075 (3)	4.172 (5)
Cu1—Na1^xxv	919.1 (11)	3.738 (8)	6.149 (5)
Cu1—Na1^xix	995.9 (9)	3.365 (4)	6.564 (5)
Cu1—Na1^xx	632.8 (10)	2.641 (9)	3.374 (6)
Cu1—Na1^xxvi	854.5 (10)	3.183 (9)	5.329 (5)
O1—O1ⁱ	2.789 (11)	2.668 (14)	3.008 (15)
O1—O1ⁱⁱ	2.789 (11)	2.668 (14)	3.008 (15)
O1—O1ⁱⁱⁱ	4.355 (13)	4.267 (11)	4.484 (16)
O1—O1^iv	4.354 (13)	4.267 (11)	4.484 (16)
O1—O1^v	4.355 (13)	4.267 (11)	4.484 (16)
O1—O1^vi	4.355 (13)	4.267 (11)	4.484 (16)
O1—O1^xii	3.795 (11)	3.729 (13)	3.862 (12)
O1—O1^xxvii	4.354 (13)	4.116 (11)	4.474 (15)
O1—O1^xiii	2.575 (11)	2.50 (2)	2.654 (14)
O1—O1^xiv	3.346 (13)	3.301 (17)	3.39 (2)
O1—O1^xv	3.795 (11)	3.729 (13)	3.862 (12)
O1—O1^xvi	4.353 (13)	4.116 (11)	4.474 (15)
O1—O1^xviii	4.871 (11)	4.633 (13)	5.051 (13)
O1—O1^xix	4.871 (11)	4.633 (13)	5.051 (13)
O1—O1^xxviii	3.783 (10)	3.640 (8)	4.067 (12)
O1—O1^xxii	3.784 (10)	3.640 (8)	4.067 (12)
O1—Na1^vii	952.7 (19)	4.578 (14)	5.444 (11)
O1—Na1^viii	1076 (2)	4.578 (14)	6.169 (9)
O1—Na1ⁱ	998 (2)	3.507 (11)	6.988 (7)
O1—Na1	495 (2)	2.230 (11)	3.507 (11)
O1—Na1ⁱⁱ	695 (2)	2.257 (12)	4.620 (8)
O1—Na1^ix	1300.7 (18)	4.620 (8)	7.808 (8)
O1—Na1^v	1003.5 (19)	3.709 (9)	6.400 (7)
O1—Na1^vi	542 (2)	2.189 (7)	3.709 (9)
O1—Na1^xi	706.7 (19)	2.189 (7)	4.981 (8)
O1—Na1^xxiv	1344.1 (18)	4.981 (8)	8.486 (8)
O1—Na1^xiii	980 (2)	4.193 (12)	5.889 (10)
O1—Na1^xv	841 (2)	3.93 (2)	4.693 (14)
O1—Na1^xvii	1208 (2)	4.693 (14)	7.635 (9)
O1—Na1^xxvii	1293.3 (17)	4.749 (8)	7.933 (8)
O1—Na1^xiv	680.0 (19)	2.250 (10)	4.749 (8)
O1—Na1^xvi	481.1 (19)	2.220 (9)	3.246 (9)
O1—Na1^xxv	989.6 (18)	3.246 (9)	6.769 (7)
O1—Na1^xix	941.6 (17)	3.799 (7)	5.978 (8)
O1—Na1^xx	826.8 (17)	3.756 (15)	4.811 (7)
O1—Na1^xxvi	1184.5 (18)	4.781 (10)	7.023 (8)
O1—Na1^xxix	1062 (2)	4.480 (8)	6.457 (10)
O1—Na1^xxx	960 (2)	4.480 (8)	5.339 (14)
O1—Na1^xxii	1091 (2)	4.625 (10)	6.823 (9)
O1—Na1^xxxi	962.3 (19)	4.446 (6)	5.236 (11)
Na1—Na1ⁱ	3.553 (7)	3.059 (10)	4.233 (10)
Na1—Na1ⁱⁱ	3.549 (7)	3.059 (10)	4.233 (10)
Na1—Na1ⁱⁱⁱ	5.444 (9)	4.811 (11)	5.758 (7)
Na1—Na1^iv	4.163 (9)	3.639 (18)	4.617 (17)
Na1—Na1^xxxii	5.444 (9)	4.811 (11)	5.758 (7)
Na1—Na1^v	5.444 (9)	4.811 (11)	5.758 (7)
Na1—Na1^vi	4.161 (9)	3.639 (18)	4.617 (17)
Na1—Na1^xi	5.440 (9)	4.811 (11)	5.758 (7)
Na1—Na1^xiv	2.982 (8)	2.550 (6)	3.197 (9)
Na1—Na1^xvi	2.980 (8)	2.550 (6)	3.197 (9)
Na1—Na1^xix	4.453 (8)	4.347 (9)	4.534 (7)
Na1—Na1^xxix	3.064 (10)	3.029 (9)	3.088 (9)
Na1—Na1^xx	4.453 (8)	4.347 (9)	4.534 (7)
Na1—Na1^xxx	3.064 (10)	3.029 (9)	3.088 (9)

Selected bond lengths (Å) for (II) top

	Average	Minimum	Maximum
Cu1—Cu1ⁱ	2.7895	2.7577	2.8181
Cu1—Cu1ⁱⁱ	2.7895	2.7577	2.8181
Cu1—O1	1.8991	1.8579	1.9298
Cu1—O1ⁱⁱ	1.8991	1.8579	1.9298
Cu1—Na1ⁱⁱⁱ	17.5745	3.0599	4.1968
Cu1—Na1	20.3621	3.2115	5.1372
Cu1—Na1ⁱⁱ	15.7315	2.8961	3.776
Cu1—Na1^iv	20.5305	3.2528	5.1985
Cu1—Na1^v	15.6325	2.738	3.3056
Cu1—O11	1.9004	1.8332	1.9504
Cu1—O11ⁱⁱ	1.9004	1.8332	1.9504
Cu1—Na11ⁱⁱ	16.2516	2.8958	3.8568
Cu1—Na11^vi	19.3148	3.0749	4.7487
Cu1—Na11^vii	18.0009	3.1054	4.1987
Cu1—Na11^viii	15.6102	2.8067	3.4583
Cu1—Na11^ix	19.4405	3.2627	5.1377
O1—O1ⁱ	2.7886	2.709	2.8845
O1—O1ⁱⁱ	2.7886	2.709	2.8845
O1—Na1	13.4019	2.2948	3.6968
O1—Na1ⁱⁱ	15.5059	2.3242	4.3988
O1—Na1^iv	14.3695	2.2962	3.7564
O1—Na1^v	15.8104	2.2962	3.8109
O1—O11	2.5776	2.5176	2.654
O1—O11^x	3.3653	3.3482	3.3886
O1—Na11^x	18.6881	2.3551	4.8118
O1—Na11^vii	11.6155	2.2979	2.3551
O1—Na11^xi	21.7372	3.0006	5.4042
Na1—Na1ⁱ	3.4932	3.0793	3.9071
Na1—Na1ⁱⁱ	3.4932	3.0793	3.9071
Na1—O11^x	9.3842	2.2772	2.4236
Na1—O11^vii	10.7287	2.3301	3.6216
Na1—Na11^x	2.9994	2.7945	3.1618
Na1—Na11^vii	2.9994	2.7945	3.1618
Na1—Na11^xii	3.0505	2.9911	3.1095
Na1—Na11^xiii	3.0505	2.9911	3.1095
O11—O11ⁱ	2.792	2.6948	3
O11—O11ⁱⁱ	2.792	2.6948	3
O11—Na11	19.025	2.5664	4.7373
O11—Na11ⁱⁱ	11.9068	2.3115	2.5664
O11—Na11^vi	22.0161	3.1755	5.5575
O11—Na11^xiv	19.4868	2.7714	5.1699
O11—Na11^viii	12.0532	2.2831	2.7714
Na11—Na11ⁱ	3.4961	3.0733	3.8669
Na11—Na11ⁱⁱ	3.4961	3.0733	3.8669

Selected bond lengths (Å) for (III) top

	Average	Minimum	Maximum
Cu1—Cu1ⁱ	2.797 (3)	2.781 (4)	2.812 (4)
Cu1—Cu1ⁱⁱ	2.796 (3)	2.781 (4)	2.812 (4)
Cu1—O1	1.919 (10)	1.857 (12)	1.982 (10)
Cu1—O1ⁱⁱ	1.918 (10)	1.857 (12)	1.982 (10)
Cu1—O1ⁱⁱⁱ	1.919 (10)	1.857 (12)	1.982 (10)
Cu1—O1^iv	1.918 (10)	1.857 (12)	1.982 (10)
Cu1—Na1	376.3 (8)	2.876 (8)	4.854 (7)
Cu1—Na1ⁱⁱ	331.7 (8)	2.876 (8)	4.020 (9)
Cu1—Na1^v	318.7 (6)	2.548 (10)	3.927 (6)
Cu1—Na1^iv	312.9 (8)	2.876 (8)	3.805 (7)
Cu1—Na1^vi	313.0 (6)	2.548 (10)	3.366 (6)
O1—O1ⁱ	2.795 (13)	2.733 (16)	2.915 (16)
O1—O1ⁱⁱ	2.794 (13)	2.733 (16)	2.915 (16)
O1—O1ⁱⁱⁱ	2.625 (14)	2.54 (3)	2.711 (18)
O1—Na1	248.1 (14)	2.175 (13)	3.384 (12)
O1—Na1ⁱⁱ	345.2 (13)	2.214 (14)	4.592 (10)
O1—Na1^vii	266.2 (12)	2.147 (9)	3.710 (11)
O1—Na1^v	346.0 (12)	2.147 (9)	4.741 (9)
O1—Na1^viii	339.6 (12)	2.231 (13)	4.689 (9)
O1—Na1^ix	243.6 (12)	2.210 (12)	3.264 (11)
Na1—Na1^viii	3.038 (9)	2.656 (7)	3.228 (10)
Na1—Na1^ix	3.036 (9)	2.656 (7)	3.228 (10)

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